Insecticide, fungicide, and the like



and deals with a new class of compounds which E are particularly advantageous for such uses. I 7 V 9 One object of the invention is toprovide a s 5 material which is convenient to ship, store and I handle and which can be effectively used for inmmethyl fm sulfide secticidal} fungicidal and bactericidal purposes. CE:

I haveiound that sulfides containing at least it) one sulfur atom attached to two carbon atoms 10 which are joined in a saturated carbon chain, S and especially those having a sulfur atom attetramethyl ethylene sulfide tached to two directly connected carbon atoms CH CH e. g. sulfides containing the group \C CHr- V Cl 3a I 15 v \B I trime vlene sulfide are particularly effective for the said. purposes. 2 sulfides of this type may be derived from either p s g0 unsaturated aliphatic or alicyclic hydrocarbons and not only may the sulfides themselves be used 3 but also suitable-derivatives thereofand homologous saturated aliphatic sulfides, as

Typical sulfides which may be used in well as the similar unsaturated aliphatic-sulfides 25. cordance with my invention include, for example, such as butadlene monosumde an alkyl sulfides, such as ethylene sulfide s a propylene smnde isoprene monosulfide 80 cn,-cH-cm V 5 I taupe-05 021- symmetrical dimethyl ethylene sulfide s I CI-Ir-CH-CH-CH; and the like, and the corresponding polysulfides 35 f as butadiene disulfide isobutylene sulfide 3 7 57 CH, SV 8 40 CHw-t'J-CH. etc. Also suitable are the analogous sulfides of 40 cyclic compounds including both aliphatic alnd m 1e, as c c od butylene sulfide gigriggisutlagniiiounds, such for exa p y I cm p 0 cm cm-Jm-cm-cn.

v c e11.

CHr-CH a amylene sulfide ';7 styrene sulfide 7 g symmetrical methyl ethyl ethylene sulfide ogj n Patented Dec. 194) I I i I UNITED STATES PATENT OFFICE INSECTICIDE, FUNGICIDE, AND THE Henrlcus Jacobus Charles Tendeloo, The Hague, Netherlands, assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware j 1 A NmDrawing. Application March 26, 1-937, Sell'gzlsNo. 133,185. In the Netherlands April 20,

8 Claims. (01. 167-33) This invention relates to materials useful for isopropyl ethylene sulfidedestroying vermin and other noxious organisms CHr-CH--CHCHr-CH: I u s and the like. sulfides containing substituents 2 such as halogen, #41112, on, COOH, --CN, ASH2, etc., as oxypropylene sulfide I nof-cnrcn-s- -cm monochlor ethylene sulfide CIS-7C;H' C| andthe like, may be used in place of or admixed with, the unsubstituted sulfide or sulfides chosen. These sulfides may be applied as the chemical individuals or as mixtures thereof or as crude materials containing other compounds which may or may not have a similar action under the conditions of application, such, for example, as the mixtures of sulfides and dithlocyanates obtainable as crude products in one method of manufacturing thesulfides. Other substances, which ma act solely as diluents or carriers, such as hydrocarbons, kieselguhr, etc., or which may possess desirable insecticidal, fungicidal or bactericidal properties, as HCN, CS2, epoxyethane or the like, may be added to the sulfide or sulfides chosen,.either before or at the time of application. In general, the sulfides used in my insecticidal preparations, may be manufactured by reaction of suitable dithiocyanates with a solution of NazS containing NaHS, a process described, for example, by Delpine in the Bull. Soc. Chim. (4) 27, 740 (1920). It has been found desirable to avoid as much as possible any substantial rise in temperature during the process, and not as generally recommended in the literature, to separate the product from the reaction mixture by distillation with steam, but to isolate it from the re: action mixture by means of vacuum distillation at a low temperature. As the before mentioned sulfides, especially the lower sulfides are somewhat unstable, they are preferably used'together with suitable amounts of stabilizing agents such as phenols, etc.

The lower molecular sulfides are in general volatile. substances which evaporate readily and have been found to be eminently suitable for use as so-called gassing insecticides. As such they may be effectively used in destroying insects in food stuffs and in fumigating warehouses, dwellings and ships as well as for the destruction of vermin on 'human beings and animals. The higher molecular sulfides are less volatile and may, therefore, be more suitably used as contacting. or stomachal insecticides, e. g. for combating plant lice and in orchardsprays, etc'., for protection against aphids, scale, etc.

For the purpose of making my invention more clear itwill be further described with more parti ular reference to the use of ethylene sulfide awn me sulfides. It will be understood that this imp e's no limitation on my invention. however, as the other sulfides already referred to are also eflective in similar and other suitable applications. a

Because of its low boiling point (55 C.) and its exceptional activity ethylene sulfide is especially useful for insecticidal and analogous purposes. "Its activity is such that it may be used effectively at. lo'w'concentrations which lie outside the explosive limits. For this reason it makes a desirable substitute for carbon disulfide fumigants and cumin fact be safely employed where the fire hazard of the latter makes it too dangerous to use. In comparative tests on cockroaches. ethylene sulfide was found to be about'twenty times as effective as ethylene oxide. In a representative test ethylene sulfide was introduced into a closed volume of airto a concentration of only 0.1%. At this low concentration the cockroaches My invention is not only capable of wide variation with respect tothe type of organic sulfide having a sulfur atom attached to two carbon atoms joined in a saturated carbon chain,

which may be used, but also with respect to the 3 character of organisms whichinay be controlled therewith, asl these also include flies, gnats, mosquitoes, weevils, beetles and the like. It will therefore be clear that my invention is not to be regarded as limited to'the details of operation described, but only by the terms of the accompanying claims, in which it is my intention to claim all novelty inherent therein as bro 3 as is possible in view of the prior art.

I claim as my invention; v 1. Asan insecticide, fungicide, bactericide and the like, a preparation containing as an active ingredient an organic sulfide having at least one 'sulfur atom attached to two directly-connected carbon atoms.

- 2. As an insecticide, fungicide, bactericide and the like, a preparation containing as an active.

ingredient an aliphatic monomeric organic sulfide liaving a sulfur atom attached to two directly connected carbon atoms which are joined in a saturated carbon chain.

'3. An insecticide composition containing an effective amount of an alkyl sulfide having a sulfur atom attached to two directly connected saturated carbon atoms.

-, 4. An insecticide containing as an active ingredient an unsaturated aliphatic sulfide having a sulfur atom attached totwo directly connected saturated carbon atoms.

5. An insecticide containing asan active ingradient a carbocyclic sulfide having a sulfur atom attached to two'directly connected saturated carbon atoms. I

- 6. A fumigant comprising an effective amount of ethylene sulfide.

. 7. A fumigant comprising an effective amount of a butylene sulfide.

8. As an insecticide, fungicide, bactericide and the like, a preparation containing as an active ingredient an aliphatic monomeric organic sulfide having a sulfur atom attached to two carbon atoms which are joined in a saturated carbon chain through an ethylene radical.

' unisia-Ices JACOBUS CHARLES'TENDELOQ' 

